Palladium catalysis Pd

Aniline nucleophiles readily participate in this type of ring-closure process under palladium catalysis (Pd(OAc>2, BINAP, and CS2CO3 in hot toluene) without resort to protecting groups when an aryl iodide is used <2005T61>. 

To conclude this part of this section, we include an interesting study that was reported in 2012 by Ikawa et al. [141], in which phenols treated with nonafluorobutenesulfonyl fluoride (where Nf=S02(CF2)3CF3) underwent the Suzuki-Miyaura reaction in moderate yields under palladium catalysis (Pd(OAc)2 or Pd2(dba)3), using SPhos as the ligand and a weak base. The reaction proceeds through nonaflation of the phenols, that is, via an activated nonafluorobutanesulfonyl intermediate. 

Comparing to C(sp )-H, the activation of C(sp )-H bonds was not difficult. Buchwald developed a method in which the combination of an amide and an unactivated arene [19], under palladium catalysis (Pd(OAc)2), can be used to efficiently produce a series of carbazoles with the aid of a directing functional group. The derivatives of carbazoles have important photophysical and biological... 

Transition-Metal Catalyzed Cyclizations. o-Halogenated anilines and anilides can serve as indole precursors in a group of reactions which are typically cataly2ed by transition metals. Several catalysts have been developed which convert o-haloanilines or anilides to indoles by reaction with acetylenes. An early procedure involved coupling to a copper acetyUde with o-iodoaniline. A more versatile procedure involves palladium catalysis of the reaction of an o-bromo- or o-trifluoromethylsulfonyloxyanihde with a triaLkylstaimylalkyne. The reaction is conducted in two stages, first with a Pd(0) and then a Pd(II) catalyst (29). 

Bromoalkynes also couple with vinylstannanes readily to result in enynes. Synthesis of protected enynals via cross-coupling of vinylstannanes with 1-bromoalkynes in the presence of a catalytic amount of Pd(II) has been reported (equation 143)252. Hiyama and coworkers extended the Stille methodology for sequential three-component coupling of trimethylstannyl(trimethylsilyl)acetylene with a vinyl iodide in the first step and cross-coupling of the intermediate trimethylsilylethyne with another alkenyl iodide in the presence of tris(diethylamino)sulphonium trimethyldifluorosilicate in the second step to generate a dienyne (equation 144)253. Both steps occur under palladium catalysis, in one-pot, to result in stereodefined l,5-dien-3-ynes. 

The intramolecular arylation of sp3 C-H bonds is observed in the reaction of l-/ r/-butyl-2-iodobenzene under palladium catalysis (Equation (71)) 94 94a 94b The oxidative addition of Arl to Pd(0) gives an ArPdl species, which undergoes the electrophilic substitution at the tert-butyl group to afford the palladacycle. To this palladacycle, another molecule of Arl oxidatively adds, giving the Pd(iv) complex. 

Lin and Yamamoto described a Pd-catalyzed carbonylation of benzyl alcohols [131]. Thus, under the agency of palladium catalysis and promotion by HI, 3-thiophenemethanol was carbonylated to give 3-thiopheneacetic acid as a major product along with methylthiophene as a minor one. 

The formation of an s/Z-hybridized C—P bond is readily achievable using the Michaelis-Arbuzov reaction. Such an approach is not applicable to form heteroaryl C—P bonds in which the carbon atoms are sp2 hybridized, whereas palladium catalysis does provide a useful method for Csp2—P bond formation. The first report on Pd-catalyzed C—P bond formation was revealed by Hirao et al. [134-136]. Xu s group further expanded the scope of these reactions [137, 138], They coupled 2-bromothiophene with n-butyl benzenephosphite to form n-butyl arylphosphinate 161 [137]. In addition, the coupling of 2-bromothiophene and an alkylarylphosphinate was also successful [138], For the mechanism, see page 19-21. 

The mechanism of propene/CO copolymerisation by palladium catalysis is essentially analogous to those of ethene and styrene (i. e., chain propagation proceeds via alternating insertions of CO into Pd-alkyl and alkene into Pd-acyl controlled by p-chelates) [1]. 

The sole report of homogeneous palladium catalysis invoking vinylidene intermediates comes from the laboratory of Buono and coworkers [38]. They discovered a reaction unique to air-stable palladium catalysts 122, which form from the self-assembly of secondary phosphine oxides with Pd(II) (Equation 9.12). 

Recently, Fu and coworkers have shown that secondary alkyl halides do not react under palladium catalysis since the oxidative addition is too slow. They have demonstrated that this lack of reactivity is mainly due to steric effects. Under iron catalysis, the coupling reaction is clearly less sensitive to such steric influences since cyclic and acyclic secondary alkyl bromides were used successfully. Such a difference could be explained by the mechanism proposed by Cahiez and coworkers (Figure 2). Contrary to Pd°, which reacts with alkyl halides according to a concerted oxidative addition mechanism, the iron-catalyzed reaction could involve a two-step monoelectronic transfer. 

Catalyst particles generally consist of a metal deposited onto the surface of a support and are denoted by metal/support, e.g. Pd/C indicates palladium metal on a carbon support. Among the metals used for catalysis, Pd is often found to be the most active metal. (Augustine 1965) For example, in the aqueous hydrodechlorination of 1,1,2-trichloroethane, Pd catalysts achieved significantly more conversion than Pt or Rh catalysts. (Kovenklioglu et al. 1992) Catalyst supports can vary in shape, size, porosity and surface area typical materials include carbon, alumina, silica and zeolites. 

Direct allylation of rhodanine 49 (Scheme 13) under Pd(0)-catalysis with cinnamyl ethyl carbonate affords the /V-allylated compound 50. However, allylation with cinnamyl bromide and a base is not regioselective, producing a mixture of 50 and sulfide 51. Sulfide 51 isomerizes to 50 under palladium catalysis (N > S), thus indicating that Pd(0)-catalyzed allylation of 49 is thermodynamically controlled (93T1465). 

The field of homogeneous palladium catalysis traces its origin to the development of the Wacker process in the late 1950s (Eq. 7) [83]. Since this discovery, palladium-catalyzed reactions have evolved into some of the most versatile reactions for the synthesis of organic molecules [84,85]. Palladium-catalyzed Wacker-type oxidation of alkenes continues to be an active field of research [86-88], and several recent applications of NHC-coordinated Pd catalysts have been reported for such reactions. 

Oxygen heterocycles can be prepared in several different ways via palladium catalysis, even though oxygen is a poorer nucleophile than nitrogen. For example, p, y-alkynic ketones are cyclized to fhrans in the presence of Pd(dba)2 and PPhs (equation 96). 

A variety of palladium(II) and palladium(O) complexes serve as effective precatalysts or precursors to the active palladium(O) catalyst. The most commonly used precatalysts in Heck chemistry are Pd(OAc)2, Pd2(dba)3, and PdCl2(PPh3)2. Typical catalyst loading is in the range of 5-10mol-%. The discovery of the unique catalytic activity of a dimeric palladacycle (Pd2(P(o-Tol)3)( Li-OAc)2) by Herrmann and Belle/ has set a milestone in palladium catalysis as it allows the use of even unreactive chloroaryl substrates intransformations. 

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